Resin additive composition and process for producing the same

ABSTRACT

In this application is disclosed a resin additive composition which can by produced by precipitating a calix(n+m+l)arene represented by the following general formula (2) and in a dissolved state together with or at the same time at least one functional ingredient selected from the group consisting of various water-soluble or hydrophilic resin flam-retardants, resin thermal stabilizers and resin curing agents, and in a dissolved or suspended state.  
                 
 
     This resin additive composition has a good affinity for organic polymers such as polyolefin and the like, which allows the functional ingredient(s) to be dispersed homogeneously in the resin. Therefore are provided high-performance resin compositions comprising various functional ingredient(s).

TECHNICAL FIELD

[0001] The present invention relates to a novel resin additivecomposition, and a process for producing the same. Also, the presentinvention relates to a resin composition blended with the resin additivecomposition, and a thermally plasticized product or thermally curedproduct thereof.

BACKGROUND ART

[0002] Recently, green polymers including polyolefins as therepresentative have become very important as the severity of globalenvironmental problems increases. In order to expand the applicationrange of polyolefins, it is actively studied to improve the physicalproperties of polyolefins per se.

[0003] On the other hand, the improvement of performance of polyolefinsby incorporating a functional ingredient into the polyolefins is apotent means for expanding their application range and therefore hasattracted attention from every side. However, since polyolefins arehydrophobic, various water-soluble or hydrophilic functional ingredientsexhibit a poor affinity to polyolefins as they are, so that it isdifficult to disperse such ingredients in such polymers. Therefore,Japanese Patent Application Laid-Open (Kokai) No. 203906/1998, forexample, discloses an antibacterial agent wherein an antibacterial metalions are included in and supported by a calixarene, and also describesthat the antibacterial agent exhibits a good affinity to organicpolymers. Moreover, although it is not aimed at to disperse in apolymer, Japanese Patent Application Laid-Open (Kokai) No. 249941/1991discloses a deodorant composition wherein a divalent metal salt isincluded in a calixarene.

DISCLOSURE OF THE INVENTION

[0004] It is an object of the present invention to provide a resinadditive composition comprising a functional ingredient such as various,water-soluble or hydrophilic flame retardants, and a process forproducing the same. It is another object of the present invention toprovide a resin composition blended with the above resin additivecomposition, and a thermally plasticized product or thermally curedproduct thereof.

[0005] As a result of the extensive studies, the present inventors havefound that a functional resin additive composition excellent in anaffinity to organic polymers (herein, sometimes referred to simply as“resins”) including green polymers can be obtained by dispersinghomogeneously a functional ingredient such as a flame retardant or thelike in the solid of a calixarene, and also various functions can beimparted to organic polymers by such resin additive composition beingallowed to be included in organic polymers. Based on these findings,they have accomplished the present invention.

[0006] Accordingly, a first embodiment of the present invention relatesto a resin additive composition comprising a calix(n+m+l)arenerepresented by the following general formula (1) and a functionalingredient dispersed homogeneously in the solid of thecalix(n+m+l)arene.

[0007] wherein R₁, R₂ and R₃ represent each independently a hydrogenatom, a saturated or unsaturated alkyl group which may havesubstituent(s), an aryl group which may have substituent(s), an alkoxylgroup which may have substituent(s), a halogen atom, a nitro group, anacyl group, a carboxyl group, a sulfonic acid group or an amino groupwhich may have substituent(s), R₄ represents a saturated or unsaturatedalkyl group which may have substituent(s), an aryl group which may havesubstituent(s) or an acyl group, and n represents an integer of 0 to 10,m represents an integer of 0 to 10, l represents an integer of 0 to 10,and n+m+l represents an integer of 4 to 10. R₁, R₂ and R₃ may bedifferent from each other depending on each unit of n, m and l. M^(+k)represents a metal ion, an NH₄ ⁺ ion or an organic cation, +k representsthe valence number of the ion, and k represents an integer of 1 to 6.Z^(−i) represents an anion, −i represents the valence number of theanion, and i represents an integer of 1 to 6. x represents an integer of0 to 10 and y represents an integer of 0 to 10, which satisfy

x×k=i×y+n.

[0008] According to the present invention, calix(n+m+l)arenes arepreferably those compounds wherein M^(+k) represents an alkali metalion, an NH₄ ⁺ ion or an organic ammonium, that is, k represents 1, inthe above general formula (1).

[0009] According to the present invention, calix(n+m+l)arenes arepreferably those compounds wherein, in the general formula (1), m is 0,and n+m+l represents 4, 6 or 8, and R₁ and R₃ represent each a hydrogenatom and R₂ represents a saturated or unsaturated alkyl group which mayhave substituent(s) or an aryl group which may have substituent(s).

[0010] Moreover, according to the present invention, calix(n+m+l)arenesare preferably those compounds wherein, in the general formula (1), m isan integer of 1 or more, and n+m+l represents 4, 6 or 8, and R₁ and R₃represent each a hydrogen atom and R₂ represents a saturated orunsaturated alkyl group which may have substituent(s) or an aryl groupwhich may have substituent(s).

[0011] The functional ingredient to prepare a functional resin additivecomposition by being dispersed homogeneously in the solid of thecalixarene described as above is a resin flame retardant, a resinthermal stabilizer, and a resin curing agent.

[0012] Furthermore, a second embodiment of the present invention relatesto a process for producing the above functional resin additivecomposition. Briefly, the process comprises a step of precipitating acalixarene in a dissolved state together with a functional ingredient ina dissolved or suspended state, for example, in the form where thefunctional ingredient is held between the molecules of the calixarene.

[0013] Specifically, it relates to a process for production wherein asolution or suspension of a functional ingredient such as a flameretardant or the like in a solvent containing water and/or an alcohol ora solvent capable of mixing with them is blended with a solution of acalix(n+m+l)arene represented by the following general formula (2) in asolvent containing an alcohol, whereby a precipitate is formed, and theresulting solid matter (precipitate) is separated from the liquid byfiltration or the like.

[0014] wherein R₁, R₂ and R₃ represent each independently a hydrogenatom, a saturated or unsaturated alkyl group which may havesubstituent(s), an aryl group which may have substituent(s), an alkoxylgroup which may have substituent(s), a halogen atom, a nitro group, anacyl group, a carboxyl group, a sulfonic acid group or an amino groupwhich may have substituent(s), R₄ represents a saturated or unsaturatedalkyl group which may have substituent(s), an aryl group which may havesubstituent(s) or an acyl group, and n represents an integer of 1 to 10,m represents an integer of 0 to 10, 1 represents an integer of 0 to 10,and n+m+l represents an integer of 4 to 10. R₁, R₂ and R₃ may bedifferent from each other depending on each unit of n, m and l. M^(+k)represents a metal ion, an NH₄ ⁺ ion or an organic cation, +k representsthe valence number of the ion, and k represents an integer of 1 to 6.Z^(−i) represents an anion, −i represents the valence number of theanion, and i represents an integer of 1 to 6. x represents an integer of1 to 10 and y represents an integer of 0 to 10, which satisfy

x×k=i×y+n.

[0015] By the way, the difference between the both formulae of the abovegeneral formula (1) and the general formula (2) lies in each range of nand x in the both formulae. That is, the difference is whether theformulae include the case of n=0 or x=0, or not. The reason why such adifference arises because the general formula (1) represents thecalixarene in the produced resin additive composition of the presentinvention, but the general formula (2) represents the calixarenesolubilized in a solvent upon the production of the resin additivecomposition of the present invention.

[0016] In greater detail, upon the production of the resin additivecomposition of the present invention, the calixarene represented by theabove general formula (2) should be solubilized in a solvent, wherein nis necessarily 1 or more, i.e., phenol group(s) have become phenoxyion(s) by a base, and also x is 1 or more, i.e., counter ion(s) (M inthe general formula (2)) are present. Thereafter, in the operation, thecalixarene is precipitated together with the functional ingredient. Onthe other hand, upon the production of the resin additive composition,in the case that neutralization with an acid is carried out, the phenoxyion(s) revert to the phenol form and thus there is a possibility thatthe counter ion(s) are not necessary, so that there is the case of x=0or n=0. Therefore, in that case, the calixarene is present in theproduced resin additive composition in such a form, that is, the form ofn=0 or x=0 which is represented by the general formula (1).

[0017] Furthermore, a third embodiment of the present invention relatesto a resin composition blended with the above resin additivecomposition, and a thermally plasticized product or thermally curedproduct of such a resin composition.

[0018] In the following will be described the present invention indetail.

[0019] In the resin additive composition containing the functionalingredient relating to the first embodiment of the present invention, afunctional ingredient such as a flame retardant or the like is containedby homogeneously dispersed in the solid of a calix(n+m+l)arenerepresented by the above general formula (1).

[0020] In the above general formula (1), as has been describedpreviously, R₁, R₂ and R₃ represent each independently a hydrogen atom,a saturated or unsaturated alkyl group which may have substituent(s), anaryl group which may have substituent(s), an alkoxyl group which mayhave substituent(s), a halogen atom, a nitro group, an acyl group, acarboxyl group, a sulfonic acid group or an amino group which may havesubstituent(s).

[0021] As such a saturated or unsaturated alkyl group which may havesubstituent(s), there may be mentioned, e.g., methyl, ethyl, propyl,isopropyl, butyl, iso-butyl, sec-buthyl, tert-butyl, pentyl, hexyl,2-ethylhexyl, octyl, or tert-octyl group, or the like. Out of these,lower alkyl groups having at most about 10 carbon atoms such asisopropyl, or tert-butyl group, and the like, are preferred. Also,allyl, 1-propenyl and the like groups may be mentioned.

[0022] There may be also mentioned a carboxyl-substituted alkyl groupsuch as carboxymethyl, carboxyethyl, carboxypropyl, carboxylbutyl or thelike; a alkoxycarbonyl alkyl group such as methoxycarbonylmethyl,ethoxycarbonylmethyl or the like; a hydroxyl-substituted alkyl groupsuch as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl or thelike; a sulfonic acid alkyl group such as sulfomethyl, sulfoethyl,sulfopropyl, sulfobutyl or the like; an amino-substituted alkyl groupsuch as aminomethyl, aminoethyl, aminopropyl, aminobutyl or the like; anaryl-substituted alkyl group such as phenethyl or the like, or the like.

[0023] As such an aryl group which may have substituent(s), there may bementioned, e.g., phenyl, tolyl, xylyl, cumenyl, 4-biphenylyl or thelike. Out of these, phenyl is preferred. As such an alkoxyl group whichmay have substituent(s), e.g., methoxyl, ethoxyl, propoxyl, butoxyl,methoxyethoxyl or the like. As such a halogen atom, there may bementioned fluorine, chlorine or bromine atom. As such an acyl group,there may be mentioned acetyl, propionyl, benzoyl or the like. As suchan amino group which may have substituent(s), there may be mentionedamino, methylamino, ethylamino, dimethylamino, diethylamino, or thelike.

[0024] Also, as has been described above, R₁, R₂ and R₃ may be differentfrom each other depending on each unit of n, m and l. R₄, as has beendescribed above, represents a saturated or unsaturated alkyl group whichmay have substituent(s), an aryl group which may have substituent(s) oran acyl group. Specific examples thereof may be the same as those whichhave been described above, in connection with R₁, R₂ and R₃.

[0025] Further, as has been described previously, n represents aninteger of 0 to 10, m represents an integer of 0 to 10, l represents aninteger of 0 to 10, and n+m+l represents an integer of 4 to 10.

[0026] As has been described above, M^(+k) represents a metal ion, anNH₄ ⁺ ion or an organic cation, +k represents the valence number of theion, and k represents an integer of 1 to 6. As the metal of such a metalion represented by M^(+k), there may be mentioned, e.g., Li, K, Na, Ca,Al, Cu, Ti, Cr, Fe, Mg, Co, Ga, Pb, Mn, Mo, Ni, Zn, Zr or the like. And,as an organic cation represented by M^(+k), there may be mentioned,e.g., a primary ammonium, a secondary ammonium, a tertiary ammonium, aquarternary ammonium, or the like. As the specific examples, there maybe mentioned C₄H₉NH₃ ⁺, (C₂H₅)₂NH₂ ⁺, (C₂H₅)₃NH⁺, (C₂H₅)₄N⁺,⁺NH₃CH₂CH₂NH₃ ⁺, pyrodinium, and the like. Out of these, an alkali metalion or NH₄ ⁺ ion represented by M^(+k) where k=1, is preferred, sincethe inventive resin additive composition can be easily obtainedtherefrom.

[0027] As has been described above, Z^(−i) represents an anion, −irepresents the valence number of the anion, and i represents an integerof 1 to 6. i represents preferably an integer of 1 to 3. As such ananion, there may be mentioned, e.g., Cl⁻, Br⁻, I⁻, SO₄ ²⁻, NO₃ ⁻, ClO₃⁻, OH⁻, OCOCH₃ ⁻, CO₃ ²⁻, CN⁻, BF₄ ⁻, HCO₃ ⁻, H₂PO₄ ⁻, HPO₄ ²⁻, PO₄ ³⁻,CNS⁻, IO₃ ⁻, SH⁻, C₂O₄ ²⁻, ClO₄ ⁻, or the like. Out of these ispreferred Cl⁻, Br⁻, OCOCH₃ ⁻, BF₄ ⁻, H₂PO₄ ⁻, HPO₄ ²⁻, PO₄ ³⁻ or thelike.

[0028] And, x represents an integer of 0 to 10 an y represents aninteger of 0 to 10, which satisfy x×k=i×y+n, as has already beendescribed.

[0029] According to the present invention, out of calix(n+m+1)arenesrepresented by the general formula (1) are preferred those compounds ofthe general formula wherein m is 0, and n+m+1 represents 4, 6 or 8, andR₁ and R₃ represent each a hydrogen atom and R₂ represents a saturatedor unsaturated alkyl group which may have substituent(s) or an arylgroup which may have substituent(s), as has been described previously.Out of these calixarenes are more preferred those of the general formulawherein R₂ represents, e.g., a lower alkyl group such as isopropyl,n-pentyl, n-octyl, tert-butyl or the like, or phenyl.

[0030] Moreover, according to the present invention, out ofcalix(n+m+1)arenes represented by the general formula (1) are preferredthose compounds of the general formula wherein m is an integer of 1 ormore, and n+m+1 represents 4, 6 or 8, and R₁ and R₃ represent each ahydrogen atom and R₂ represents a saturated or unsaturated alkyl groupwhich may have substituent(s) or an aryl group which may havesubstituent(s), as has been already described. Out of these calixarenesare more preferred those of the general formula wherein R₂ represents,e.g., isopropyl, n-pentyl, n-octyl, tert-butyl or the like, or phenyl,and R₄ represents, e.g., a lower alkyl group such as n-propyl, n-butylor the like, or acetyl or phenyl group.

[0031] According to the present invention, the above-mentioned threekinds of functional ingredients, i.e., resin flame retardant, resinthermal stabilizer and resin curing agent, are appropriately selecteddepending on the purpose, and dispersed in the solid of a calixarene. Ithas been, hitherto, difficult to disperse a water-soluble or hydrophilicfunctional ingredient in organic polymers such as polyolefins or thelike. However, the functional resin additive composition of the presentinvention can be dispersed in organic polymers, and as a result, variousfunctions can be imparted to such organic polymers.

[0032] Moreover, it is possible for two or more kinds of functionalingredients to be included or incorporated in the resin additivecomposition of the present invention. By incorporating two or more kindsof functional ingredients, a synergistic effect can be attained, whichresults in an additive composition of high performance.

[0033] Since various known functional ingredients can be employed as thethree kinds of functional ingredients according to the presentinvention, in the following will be illustrated only representativeones. That is, the following are examples of the functional ingredients,and the functional ingredients according to the present invention arenot limited thereto.

[0034] First, examples of the resin flame retardant as the functionalingredient include various boric acid-type flame-retarding compounds,phosphorus-type flame-retarding compounds, nitrogen-type flame-retardingcompounds, halogen-type flame-retarding compounds, organicflame-retarding compounds, colloidal flame-retarding compounds and thelike.

[0035] As such boric acid-type flame-retarding compounds, there may bementioned, e.g., boric acid-containing compounds such as boric acid,sodium borate, potassium borate, zinc borate hydrate, barium metaborateand borax, and the like.

[0036] As such phosphorus-type flame retarding compounds, there may bementioned, e.g., phosphorus-containing compounds such as phosphoricacid, polyphosphoric acid, sodium phosphate, potassium phosphate, sodiumpolyphosphate, potassium polyphosphate, ammonium phosphate, ammoniumpolyphosphate, melamine phosphate, red phosphorus, phosphate esters,tris(chloroethyl) phosphate, tris(monochloropropyl) phosphate,tris(dichloropropyl) phosphate, triallyl phosphate,tris(3-hydroxypropyl) phosphate, tris(tribromophenyl) phosphate,tris·β-chloropropyl phosphate, tris(dibromophenyl) phosphate,tris(tribromoneopentyl) phosphate,tetraxis(2-chloroethyl)ethylene•diphosphate, dimethylmethyl phosphate,tris(2-chloroethyl) orthophosphate, aromatic group-condensed organicphosphate esters, halogen-containing condensed organic phosphate esters,ethylene·bis·tris(2-cyanoethyl)phosphonium bromide, ammoniumpolyphosphate, β-chloroethyl acid phosphate, butyl pyrophosphate, butylacid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate,melamine phosphate salt, halogen-containing phosphates, phenylphosphonicacid, and the like.

[0037] As other inorganic flame retarding compounds, there may bementioned, e.g., halogen-type inorganic salts such as sodium bromide,potassium bromide, ammonium bromide, ammonium chloride, potassiumchloride, sodium iodide, potassium iodide, ammonium iodide and the like;metal sulfate compounds such as zinc sulfate, potassium hydrogensulfate, aluminum sulfate, antimony sulfate, sulfate esters, potassiumsulfate, cobalt sulfate, sodium hydrogen sulfate, iron sulfate, coppersulfate, sodium sulfate, nickel sulfate, barium sulfate, magnesiumsulfate and the like; ammonium-type flame retarding compounds such asammonium sulfate and the like; iron oxide-type smoke-reducing agentssuch as ferrocene and the like; metal nitrate compounds such as coppernitrate and the like; titanium-containing compounds such as titaniumoxide and the like; guanidine-type compounds such as guanidine sulfamateand the like; and in addition, zirconium compounds, molybdenumcompounds, tin compounds, carbonate salt compounds such as potassiumcarbonate and the like, metal hydroxides such as aluminum hydroxide,magnesium hydroxide and the like and modified compounds thereof; and thelike.

[0038] As such nitrogen-type flame retarding compounds, there may bementioned, e.g., melamine compounds such as melamine, melamine sulfate,melamine phosphate and the like; amines such as triethylamine,ethylenediamine, imidazole and the like, and phosphates or sulfatesthereof; triazine ring-containing cyanurate compounds; and the like.

[0039] As such halogen-type flame retarding compounds, there may bementioned, e.g., halogen-containing flame-retarding compounds such aschlorinated paraffins, perchlorocyclopentadecane, hexabromobenzene,decabromodiphenyl oxide, bis(tribromophenoxy)ethane, ethylene bisdibromonorbornanedicarboximide, ethylene bis·tetrabromophthalimide,dibromoethyl·dibromocyclohexane, dibromoneopentyl glycol,2,4,6-tribromophenol, tribromophenyl allyl ether, tetrabromo·bisphenol Aderivatives, tetrabromo·bisphenol S derivatives,tetradecabromo·diphenoxybenzene, tris-(2,3-dibromopropyl)-isocyanurate,2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, poly(pentabromobenzylacrylate), tribromostyrene, tribromophenylmaleimide, tribromoneopentylalcohol, tetrabromodipentaerythritol, pentabromobenzyl acrylate,pentabromophenol, pentabromotoluene, pentabromodiphenyl oxide,hexabromocyclododecane, hexabromodiphenyl ether, octabromophenol ether,octadibromodiphenyl ether, octabromodiphenyl oxide, dibromoneopentylglycol tetracarbonate, bis(tribromophenyl)fumaramide,N-methylhexabromodiphenylamine, bromostyrene, diallyl chlorendate, andthe like.

[0040] As other organic flame-retarding compounds, there may bementioned, e.g., organic sulfonic acid metal salts such as potassiumtrichlorobenzenesulfonate, potassium diphenylsulfone-3-sulfonate,potassium perfluorobutanesulfonate, and the like, chlorendic anhydride,phthalic anhydride, bisphenol A-containing compounds, glycidyl compoundssuch as glycidyl ether and the like, polyhydric alcohols such asdiethylene glycol, pentaerythritol and the like, modified carbamides,silicone compounds such as silicone oils, organosiloxanes and the like,and the like.

[0041] As such colloidal flame-retarding compounds, there may bementioned, e.g., colloids of hitherto used flame-retarding compoundsincluding metal hydrate compounds such as aluminum hydroxide, magnesiumhydroxide, calcium hydroxide and the like, calcium aluminate, gypsumdihydrate, zinc borate, barium metaborate, borax, hydrates such askaolin clay and the like, nitrate compounds such as sodium nitrate andthe like, molybdenum compounds, zirconium compounds, antimony compounds,dawsonite, phlogopite and the like.

[0042] Next, as such resin thermal stabilizers, there may be mentioned,e.g., the following. That is, as organic compounds, metal salts of fattyacids (metal soaps) such as zinc stearate, calcium stearate, bariumstearate and the like; polyol compounds such as pentaerythritol,dipentaerythritol, 1,3-butanediol, sorbitol and the like; epoxycompounds such as epoxidated soybean oil, dioctylepoxyhexahydrophthalate and the like; β-diketones such asdibenzoylmethane, stearoylbenzoylmethane and the like, phosphitecompounds such as triphenylphosphite and the like; and the like.

[0043] Finally, as such resin curing agents, there may be mentionede.g., triethylamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, modified hexamethylenediamine,N-aminoethylpiperazine, dipropylenetriamine,3,3-dimethyl-4,4′-diaminodicyclohexylmethane,3-amino-1-cyclohexylaminopropane, heterocyclic diamines, aliphaticamine·adducts, ketimines, modified polyamines, aliphatic polyamines suchas aliphatic polyether polyamines, polyoxypropyleneamine and the like,polyamide, modified polyamide·amines such as polyamine·adducts and thelike, aromatic polyamines such as m-phenylenediamine,p,p′-diaminodiphenylmethane, p,p′-diaminodiphenylsulfone,metaxylenediamine, 1,3-bis(aminomethyl)cyclohexane and the like,dicyandiamide, phenolderivatives such as 2-dimethylaminophenol and thelike, spiroacetal diamine, polyoxyethylenediamine, spiroguanamine,polyglycolamine, tertiary amines, boron trifluoride-type complex saltssuch as boron trifluoride-monoethylamine complex salt and the like,imidazole compounds, phthalic anhydrides such as tetrahydrophthalicanhydride and the like, maleic anhydride, trimellitic anhydride, krendicanhydride, succinic acid-type compounds such as alkenylsuccinicanhydride and the like, thiourea derivatives, octyltin(I), mercaptanecompounds, hydrazide compounds, organic tin compounds such as dibutyltindiacetate and the like, and the like.

[0044] The content of the functional ingredient(s) such as a flameretardant in the calix(n+m+1)arene of the above general formula (1) isnot particularly limited since it depends on the purpose of the resinadditive composition. However, the functional ingredient(s) may besuitably used in an amount of about 0.1 to 1,000 parts by weightrelative to 100 parts by weight of the calix(n+m+1)arene.

[0045] According to the present invention, the size of the functionalingredient(s) dispersed homogeneously in the solid of ancalix(n+m+1)arene is preferably smaller than 1 μm.

[0046] According to the present invention, as the state of functionalingredient(s), there may be mentioned such form that the functionalingredient(s) are held between the molecules of the calix(n+m+1)arene.The form can be confirmed by X-ray diffraction with regard to whether itis in a coarse crystalline state or in an amorphous state having finestructure, by means of an electron microscope with regard to the shape,by EPMA with regard to the microscopic distribution of the elements, andthe like. By the way, a mere mixture of the functional ingredient(s) andthe calixarene cannot exhibit the effects of the present invention. Thisis because mere mechanical pulverization of such a mixture does notafford fine particles of submicron order, and the dispersing ability inthe resin can not be improved, which is, in turn, because of no increasein hydrophobicity which may caused by the functional ingredientmolecules being included by the calixarene and by the calixarene beingadsorbed onto the fine particle surfaces of the functionalingredient(s).

[0047] Next, in the following will be described the process forproducing the functional resin additive composition of the presentinvention.

[0048] Briefly, the process for production comprises, as has beendescribed previously, a step of precipitating a calixarene in adissolved state together with or at the same time functionalingredient(s) in a dissolved or suspended state.

[0049] Specifically, for example, a solution or suspension (Y) of afunctional ingredient in a solvent containing water and/or an alcohol ora solvent capable of mixing therewith is mixed with a solution (X) of acalix(n+m+l)arene represented by the above general formula (2) in asolvent containing an alcohol, whereby a precipitate is caused to beformed.

[0050] The solution (X) can be obtained, as a solution of thecorresponding calix(n+m+1)arene of the general formula (2) wherein n isfrom 1 to 10, for example, by suspending a calix(n+m+1)arene of theabove general formula (2) wherein n is 0 in a solvent containing analcohol, followed by adding a base thereto.

[0051] As such an alcohol, there may be used, e.g., methanol, ethanol,propanol, or the like. By “the solvent containing an alcohol” is meant asolvent composed mainly of an alcohol and capable of dissolving thecalix(n+m+1)arene when added with a base. Usually, as the solvent perse, a solvent composed solely of an alcohol may be suitably used.

[0052] As such a base, use may be made of, e.g., an alkali metalhydroxide such as KOH, NaOH or the like, ammonia water, an organic aminesuch as triethylamine, diethylamine, ethylenediamine, (C₂H₅)₄N⁺OH⁻, orthe like, or the like. Out of these are preferred KOH and NaOH becauseof their inexpensive cost and easy handling.

[0053] The solution or suspension (Y) of a functional ingredient may beobtained by dissolving or suspending a functional ingredient in asolvent containing water and/or an alcohol or a solvent capable ofmixing therewith depending on the nature of the functional ingredient.From the viewpoint of homogeneous dispersion of the functionalingredient in the calix(n+m+1)arene, the functional ingredient ispreferably in a dissolved state.

[0054] As such an alcohol, there may be used, e.g., methanol, ethanol,propanol, or the like. As such a solvent capable of mixing with waterand/or an alcohol, use may be made of, e.g., benzene, toluene, xylene,ethyl acetate, THF, DMSO, DMF, ketone-type solvent (acetone, methylethyl ketone, diethyl ketone, allyl ethyl ketone, or the like), or thelike.

[0055] The mixing of the solution or suspension (Y) with the solution(X) may be conducted by merely mixing the two. However, in the casewhere the functional ingredient has been dissolved in water, mixing ofthe two immediately results in precipitation, and therefore it ispreferable to add dropwise the solution (X) into the solution (Y).Thereby, homogeneous dispersion of the functional ingredient in thecalix(n+m+1)arene can be attained.

[0056] In the case where mere mixing of the solution or suspension (Y)with the solution (X) does not form a precipitate, an operation forcausing a precipitate to be formed is conducted.

[0057] With regard to such an operation, a precipitate can be formed byneutralizing the mixed solution with an acid, for example. Moreover, aprecipitate can be also formed by adding an organic poor solvent for theprecipitate, which solvent is miscible with water and/or an alcohol, tothe mixed solution. As such an organic poor solvent, benzene, toluene,xylene, diethyl ether or the like may be used, for example.Alternatively, there is a case where water is suitably added instead ofthe organic poor solvent. Furthermore, a precipitate can be also formedby evaporating the solvent of the mixed solution. These operations forprecipitation may be suitably selected.

[0058] Next, the resulting precipitate(solid matter) is separated byfiltration, centrifugation or the like, and then usually subjected todrying successively. After the obtaining of the precipitate and beforethe separation thereof by filtration, or the like, the alkali adheringto the precipitate may be neutralized with an acid, if necessary. Also,after the separation by filtration or the like, the solid matter iswashed, if necessary. Drying may be conducted under suitable conditionsand, for example, drying can be achieved by heat-drying at about 30 to400° C. for 0.5 to 24 hours.

[0059] The amounts of a calix(n+m+1)arene of the above general formula(2) and a functional ingredient for use in the production of thefunctional resin additive composition of the present invention, may bedetermined in consideration of the aimed-at additive composition andthus not particularly limited. However, about 0.1 to 1,000 parts byweight of the functional ingredient may be suitably used relative to 100parts by weight of the calix(n+m+1)arene of the above general formula(2), for example.

[0060] Moreover, in the case where two or more kinds of functionalingredients are planed to be incorporated, two or more kinds offunctional ingredients may be used in the preparation of the solution orsuspension (Y) of the functional ingredients.

[0061] By the above operations, the functional resin additivecomposition of the present invention can be produced.

[0062] Furthermore, the present invention also relates to a resincomposition mixed with the above functional resin additive composition.

[0063] As such resins, there may be mentioned, e.g., thermoplasticresins including polyolefins such as polyethylene, polypropylene and thelike, polystyrene, poly-p-xylylene, polyvinyl acetate, polyacrylates orpolymethacrylates such as polymethyl methacrylate (PMMA) and the like,polyvinyl chloride (PVC), polyvinylidene chloride, fluorine-typeplastics, polyacrylonitrile, polyvinyl ethers, polyvinyl ketones,polyethers, polycarbonates, polyamides, diene-type plastics,polyurethane-type plastics, acrylonitrile-butadiene-styrene copolymer(ABS), polyacetal, polyether ether ketone (PEEK), polyphenylene,polyphenylene oxide, polysulfones, silicones, natural-substance plasticssuch as cellulose-type plastics, protein-type plastics, and the like,etc.; thermosetting plastics including polyurethane resins, phenolresins, furan resins, xylene·formaldehyde resin, ketone·formaldehyderesins, urea resins, melamine resins, aniline resins, alkyd resins,unsaturated polyester resins, epoxy resins, triallylcyanurate resin,formaldehyde resin of tris(2-hydroxyethyl)isocyanurate, acrolein-typeresins, phosphonitrile dihalide-type polymer derivatives, cured resinswith dimaleimide, thermosetting resins from cyclopentadiene,crosslinking products by cyclic urea resins, triazine-type resins, etc.;and the like.

[0064] Additionally, as such resins, use may be made of various kinds ofrubbers such as ethylene propylene rubber, chloroprene rubber and thelike; crosslinked products obtainable by crosslinking polyethylene,polyvinyl acetate resin and the like with a peroxide or the like, mutualblends of the above thermoplastic resins, mutual blends of the abovethermosetting resins, blends of thermoplastic resin(s) and thermosettingresin(s), and the like.

[0065] The resin may be suitably selected in view of physical propertiesand chemical properties required according to the application purpose.

[0066] The above functional resin additive composition of the presentinvention has a good affinity to organic polymers and thus is easilykneaded with an organic polymer, whereby a resin composition wherein thefunctional additive ingredient(s) are homogeneously dispersed, can beobtained. In particular, the advantage of the present invention getsobvious in the case where an additive ingredient is to be contained in anon-polar resin such as a polyolefin, PMMA, a polycarbonate, apolyamide, a polyacetal, ABS, PEEK, polystyrene or PVC.

[0067] The content of the resin additive composition in the resincomposition is not particularly limited since it depends on theapplication purpose and the like of the resin composition. However,about 0.01 to 60 parts by weight of the resin additive composition maybe suitably used relative to 100 parts by weight of the resin, forexample.

[0068] Moreover, the resin compositions mixed with the resin additivecomposition of the present invention in various kinds of resins can bemolded according to various application purposes by subjecting to per seknown molding method such as thermal plasticizing treatment, thermalcuring treatment, or the like.

BEST MODE FOR CARRYING OUT THE INVENTION

[0069] In the following will be described the present invention morespecifically with reference to Examples, but the present invention isnot limited thereto.

EXAMPLE 1 Resin Flame-retarding Additive Composition

[0070] A transparent solution (Solution A) was prepared by suspending100 g of 4-tert-butylcalix(8)arene in a mixed solvent of 300 g ofmethanol and 700 g of acetone, and adding 12 g of KOH thereto, followedby stirring the whole mixture at room temperature. While a solution of100 g of zinc sulfate as a flame retardant dissolved in 5,000 g of waterwas vigorously stirred, Solution A was added dropwise thereto, whereby asolid matter was precipitated. The precipitate was collected byfiltration and dried by heating at 80° C. for 24 hours. The resultingdried powder was pulverized together with sodium chloride in a ballmill, and then the sodium chloride was removed by washing the pulverizedpowder with water. The washed powder was dried by heating at 80° C. for24 hours to obtain an aimed-at powder composite (resin flame-retardingadditive composition).

[0071] The resulting powder composite was hydrophobic. When 1 g of thepowder was added into 10 mL of toluene, followed by stirring the wholemass, a well dispersed and stable dispersion was obtained. When 20 g ofthe powder and 100 g of polypropylene were mixed and transformed tostrands with an extruder, the powder was well dispersed and a resincomposition having a transparent appearance was obtained.

Flame-Retarding Effect

[0072] A test piece was prepared by adding or incorporating 20 parts byweight of the above flame-retarding additive composition to or into 100parts by weight of polypropylene. The test piece was subjected to a testin accordance with the UL flame resistance test standard. As a result,it was found that it exhibited a flame resistance of UL-94-V1 level.

[0073] Furthermore, another test piece was prepared by incorporating 20parts by weight of the above flame-retarding additive composition and 5parts by weight of silica (“VN-3” manufactured by Nippon Silica) into100 parts by weight of polypropylene. The test piece was subjected to atest in accordance with the UL flame resistance test standard. As aresult, it was found that it exhibited a flame resistance of UL-94-V0level.

EXAMPLE 2 Resin Flame-Retarding Additive Composition

[0074] A transparent solution (Solution B) was prepared by suspending 20g of 4-tert-butylcalix(8)arene in a mixed solvent of 60 g of methanoland 140 g of acetone, and adding 2.4 g of KOH thereto, followed bystirring the whole mixture at room temperature. 100 g of colloidalaluminum hydroxide as a flame retardant was suspended in 5,000 g ofwater. While the suspension was stirred vigorously, Solution B was addeddropwise thereto, whereby a solid matter was precipitated. Theprecipitate was collected by filtration and dried by heating at 80° C.for 24 hours. The resulting dried powder was pulverized together withsodium chloride in a ball mill and then the sodium chloride was removedby washing the pulverized powder with water. The washed powder was driedby heating at 80° C. for 24 hours to obtain an aimed-at powdercomposite.

[0075] When 1 g of the powder was added into 10 mL of toluene and thewhole mass was stirred, a well dispersed and stable dispersion wasobtained. When 25 g of the powder and 100 g of polypropylene were mixedand transformed to strands with an extruder, a resin composition whereinthe powder was well dispersed was obtained.

Flame-Retarding Effect

[0076] A test piece was prepared by incorporating 25 parts by weight ofthe above flame-retarding additive composition into 100 parts by weightof polypropylene. The test piece was subjected to a test in accordancewith the UL flame resistance test standard. As a result, it was foundthat it exhibited a flame resistance of UL-94-V1 level.

EXAMPLE 3 Resin Flame-Retarding Additive Composition

[0077] A transparent solution (Solution C) was prepared by suspending 10g of 4-tert-butylcalix(8)arene in 200 g of acetone, and adding 6.2 g oftriethylamine thereto, followed by stirring the whole mixture at roomtemperature. While a solution of 20 g of ammonium phosphate as a flameretardant for resin dissolved in 200 g of water was vigorously stirred,Solution C was added dropwise thereto, whereby a solid matter wasprecipitated. The precipitate was collected by filtration, washed withwater, and dried by heating at 80° C. for 24 hours, whereby an aimed-atcomposite (resin flame-retarding additive composition) was obtained.

[0078] The obtained powder composite was hydrophobic. When 20 g of thepowder and 100 g of polypropylene were mixed and transformed to strandswith an extruder, the powder was well dispersed and a resin compositionhaving a transparent appearance was obtained.

Flame-Retarding Effect

[0079] A test piece was prepared by press-molding the above strands, andwas subjected to a test in accordance with the UL flame resistance teststandard. As a result, it was found that it exhibited a flame resistanceof UL-94-V1 level.

[0080] Furthermore, another test piece was prepared by incorporating 20parts by weight of the above flame-retarding additive composition and 5parts by weight of silica (“VN-3” manufactured by Nippon Silica) into100 parts by weight of polypropylene. The test piece was subjected to atest in accordance with the UL flame resistance test standard. As aresult, it was found that it exhibited a flame resistance of UL-94-V0level.

EXAMPLE 4 Resin Flame-Retarding Additive Composition

[0081] A transparent solution (Solution D) was prepared by suspending 10g of 4-tert-butylcalix(8)arene in 200 g of acetone, and adding 5 g ofethylenediamine thereto, followed by stirring the whole mixture at roomtemperature. While a solution of 20 g of phosphoric acid as a flameretardant for resin dissolved in 200 g of water was vigorously stirred,Solution D was added dropwise thereto, whereby a solid matter wasprecipitated. The precipitate was collected by filtration, washed withwater, and dried by heating at 80° C. for 24 hours, whereby an aimed-atcomposite (resin flame-retarding additive composition) was obtained.

[0082] The resulting powder composite was hydrophobic. When 20 g of thepowder and 100 g of polypropylene were mixed and transformed to strandswith an extruder, the powder was well dispersed and a resin compositionhaving a transparent appearance was obtained.

Flame-Retarding Effect

[0083] A test piece was prepared by press-molding the above strands, andwas subjected to a test in accordance with the UL flame resistance teststandard. As a result, it was found that it exhibited a flame resistanceof UL-94-V1 level.

[0084] Furthermore, another test piece was prepared by incorporating 20parts by weight of the above flame-retarding additive composition and 5parts by weight of silica (“VN-3” manufactured by Nippon Silica) into100 parts by weight of polypropylene. The test piece was subjected to atest in accordance with the UL flame resistance test standard. As aresult, it was found that it exhibited a flame resistance of UL-94-V0level.

EXAMPLE 5 Resin Flame-Retarding Additive Composition

[0085] A transparent solution (Solution E) was prepared by suspending 10g of 4-tert-butylcalix(8)arene in 200 g of acetone, and adding 6.2 g oftriethylamine thereto, followed by stirring the whole mixture at roomtemperature. While a solution of 20 g of pentaerythritol as a flameretardant for resin dissolved in 200 g of warm water was stirredvigorously, Solution E was added dropwise thereto, whereby a solidmatter was precipitated. The precipitate was collected by filtration,washed with water and dried by heating at 80° C. for 24 hours, wherebyan aimed-at composite (resin flame-retarding additive composition) wasobtained.

[0086] The obtained powder composite was hydrophobic. When 20 g of thepowder and 100 g of polypropylene were mixed and transformed to strandswith an extruder, a resin composition wherein the powder was welldispersed and having a transparent appearance was obtained.

Flame-Retarding Effect

[0087] A test piece was prepared by incorporating 5 parts by weight ofthe above composite and 20 parts by weight of the resin flame-retardingadditive composition obtained in Example 5, into 100 parts by weight ofpolypropylene. The test piece was subjected to a test in accordance withthe UL flame resistance test standard. As a result, it was found that itexhibited a flame resistance of UL-94-V0 level.

EXAMPLE 6 Resin Flame-Retarding Additive Composition

[0088] A transparent solution (Solution F) was prepared by suspending 10g of 4-tert-butylcalix(8)arene in 200 g of acetone, and adding 6.2 g oftriethylamine thereto, followed by stirring the whole mixture at roomtemperature. While a solution of 20 g of ammonium sulphate as a flameretardant for resin dissolved in 200 g of water was stirred vigorously,Solution E was added dropwise thereto, whereby a solid matter wasprecipitated. The precipitate was collected by filtration, washed withwater and dried by heating at 80° C. for 24 hours, whereby an aimed-atcomposite (resin flame-retarding additive composition) was obtained.

[0089] The obtained powder composite was hydrophobic. When 10 g of thepowder and 100 g of polycarbonate were mixed and transformed to strandswith an extruder, a resin composition wherein the powder was welldispersed and having a transparent appearance was obtained.

Flame-Retarding Effect

[0090] A test piece was prepared by press-molding the above strands.This test piece was subjected to a test in accordance with the UL flameresistance test standard. As a result, it was found that it exhibited aflame resistance of UL-94-V0 level.

EXAMPLE 7 Resin Thermal Stabilizing Additive Composition

[0091] A transparent solution (Solution G) was prepared by suspending 10g of 4-tert-butylcalix(8)arene in 200 g of acetone, and adding 6.2 g oftriethylamine thereto, followed by stirring the whole mixture at roomtemperature. While a solution of 20 g of pentaerythritol as a thermalstabilizer dissolved in 200 g of warm water was stirred vigorously,Solution G was added dropwise thereto, whereby a solid matter wasprecipitated. The precipitate was collected by filtration, washed withwater and dried by heating at 80° C. for 24 hours, whereby an aimed-atcomposite (resin thermal stabilizing additive composition) was obtained.

[0092] The obtained powder composite was hydrophobic. When 3 g of thepowder was kneaded with 100 g of polyvinyl chloride and 50 g of dioctylphthalate with a hot mill, a resin composition wherein the powder waswell dispersed and having a transparent appearance was obtained.

Thermal Stability Effect

[0093] A sheet-shape molding was obtained by kneading 100 g of polyvinylchloride, 50 g of dioctyl phthalate, 30 g of calcium carbonate, 0.8 g ofcalcium stearate, 2.2 g of zinc stearate, and 0.5 g of the powderobtained above, with a hot roll and then subjecting the resultingmixture to a press molding. When the sheet-shape molding was subjectedto a heat resistance test at 180° C. in a gear oven, the time requiredfor the color being changed to brown was found to be 150 minutes andthus the resin composition exhibited a good thermal stability.

EXAMPLE 8 Resin Curing Additive Composition

[0094] A transparent solution (Solution H) was prepared by suspending100 g of 4-tert-butylcalix(8)arene in 700 g of acetone, adding 50 g oftriethylamine as a resin-curing agent thereto, followed by stirring thewhole mixture at room temperature. While solution H was vigorouslystirred, 700 g of water was added dropwise thereto, whereby a solidmatter was precipitated. The precipitate was collected by filtration anddried by heating at 80° C. for 24 hours. The dried powder was pulverizedtogether with sodium chloride in a ball mill and then the sodiumchloride was removed by washing the pulverized powder with water. Thewashed powder was dried by heating at 80° C. for 24 hours to obtain anaimed-at powder composite (resin curing additive composition).

[0095] The resulting powder composite was hydrophobic. When 1 g of thepowder was added to 10 mL of toluene and the whole mass was stirred, awell-dispersed and stable dispersion was obtained. When 10 g of thepowder and 100 g of a bisphenol A-type epoxy resin were mixed and themixture was subjected to a heat treatment, first, at 50° C. for 6 hoursand then at 100° C. for 2 hours, whereby a crosslinking reaction wascaused, a resin composition wherein the powder was well dispersed andhaving a transparent appearance, was obtained.

Pot Life

[0096] When pot life (100° C.) of a mixture of 20 g of the powdercomposite obtained above and 100 g of a bisphenol A-type epoxy resin wasmeasured, the above mixture started curing after 2 hours. Separately,the pot life (100° C.) of a mixture of 10 g of triethylamine and 100 gof the bisphenol A-type epoxy resin was measured, and the mixturestarted curing after 30 minutes.

[0097] The above Examples are examples of a novel functional resinadditive composition of the present invention and a process forproducing the same, and a resin composition mixed with the above resinadditive composition. Other than these Examples, functional resinadditive compositions can be produced using various functionalingredients depending on the purposes. Therefore, the above Examples aremere examples in all aspects, and should not be understoodrestrictively. Furthermore, all the changes or modifications belongingto an equivalent range of the claims fall within the scope of thepresent invention.

Industrial Applicability

[0098] According to the present invention are provided a novel resinadditive composition comprising various water-soluble or hydrophilicfunctional ingredient(s), and a process for producing the same. Theadditive composition shows as high a stability as engineering plastics.Moreover, the additive composition has a good affinity for organicpolymers such as polyolefin and the like, which allows the functionalingredient(s) to be dispersed homogeneously in the resin. Therefore areprovided high-performance resin compositions comprising variousfunctional ingredient(s).

1. A resin additive composition comprising a calix(n+m+l)arenerepresented by the following general formula (1) and at least onefunctional ingredient selected from the group consisting of resinflame-retardants, resin thermal stabilizers, and resin curing agents anddispersed homogeneously in the solid of the calix(n+m+l)arene.

wherein R₁, R₂ and R₃ represent each independently a hydrogen atom, asaturated or unsaturated alkyl group which may have substituent(s), anaryl group which may have substituent(s), an alkoxyl group which mayhave substituent(s), a halogen atom, a nitro group, an acyl group, acarboxyl group, a sulfonic acid group or an amino group which may havesubstituent(s), R₄ represents a saturated or unsaturated alkyl groupwhich may have substituent(s), an aryl group which may havesubstituent(s) or an acyl group, and n represents an integer of 0 to 10,m represents an integer of 0 to 10, l represents an integer of 0 to 10,and n+m+l represents an integer of 4 to
 10. R₁, R₂ and R₃ may bedifferent from each other depending on each unit of n, m and l. M^(+k)represents a metal ion, an NH₄ ⁺ ion or an organic cation, +k representsthe valence number of the ion, and k represents an integer of 1 to 6.Z^(31 i) represents an anion, −i represents the valence number of theanion, and i represents an integer of 1 to
 6. x represents an integer of0 to 10 and y represents an integer of 0 to 10, which satisfy x×k=i×y+n.2. The resin additive composition as set forth in claim 1, whereinM^(+k) represents an alkali metal ion, an NH₄ ⁺ ion or an organicammonium, that is, k represents 1, in the above general formula (1). 3.The resin additive composition as set forth in claim 1 or 2, wherein, inthe general formula (1), m is 0, and n+m+l represents 4, 6 or 8, and R₁and R₃ represent each a hydrogen atom and R₂ represents a saturated orunsaturated alkyl group which may have substituent(s) or an aryl groupwhich may have substituent(s).
 4. The resin additive composition as setforth in claim 1 or 2, wherein, in the general formula (1), m is aninteger of 1 or more, and n+m+l represents 4, 6 or 8, and R₁ and R₃represent each a hydrogen atom and R₂ represents a saturated orunsaturated alkyl group which may have substituent(s) or an aryl groupwhich may have substituent(s).
 5. The resin additive composition as setforth in any one of claims 1-4, wherein the size of the functionalingredient(s) dispersed homogeneously in the solid of thecalix(n+m+l)arene is smaller than 1 μm.
 6. The resin additivecomposition as set forth in any one of claims 1-5, wherein thefunctional ingredient(s) are held between the molecules of thecalix(n+m+1)arene.
 7. A process for producing the resin additivecomposition as set forth in any one of claims 1-6 which comprisesprecipitating a calix(n+m+1)arene represented by the following generalformula (2) and in a dissolved state together with or at the same timeat least one functional ingredient selected from the group consisting ofresin flame-retardants, resin thermal stabilizers and resin curingagents, and in a dissolved or suspended state.

wherein R₁, R₂ and R₃ represent each independently a hydrogen atom, asaturated or unsaturated alkyl group which may have substituent(s), anaryl group which may have substituent(s), an alkoxyl group which mayhave substituent(s), a halogen atom, a nitro group, an acyl group, acarboxyl group, a sulfonic acid group or an amino group which may havesubstituent(s), R₄ represents a saturated or unsaturated alkyl groupwhich may have substituent(s), an aryl group which may havesubstituent(s) or an acyl group, and n represents an integer of 1 to 10,m represents an integer of 0 to 10, l represents an integer of 0 to 10,and n+m+l represents an integer of 4 to
 10. R₁, R₂ and R₃ may bedifferent from each other depending on each unit of n, m and l. M^(+k)represents a metal ion, an NH₄ ⁺ ion or an organic cation, +k representsthe valence number of the ion, and k represents an integer of 1 to 6.Z^(−i) represents an anion, −i represents the valence number of theanion, and i represents an integer of 1 to
 6. x represents an integer of1 to 10 and y represents an integer of 0 to 10, which satisfy x×k=i×y+n.8. The process for producing the resin additive composition as set forthin claim 7, which comprises blending a solution or suspension of saidfunctional ingredient(s) in a solvent containing water and/or an alcoholor a solvent capable of mixing therewith and a solution of acalix(n+m+l)arene represented by the above general formula (2) in asolvent containing an alcohol, whereby a precipitate is caused to beformed, and separating the resulting precipitate.
 9. The process forproducing the resin additive composition as set forth in claim 8, whichcomprises adding dropwise a solution of a calix(n+m+l)arene representedby the above general formula (2) in a solvent containing an alcohol withstirring to a solution or suspension of said functional ingredient(s) ina solvent containing water, whereby a precipitate is caused to beformed, and separating the resulting precipitate.
 10. The process forproducing the resin additive composition as set forth in claim 9,wherein after a precipitate has been caused to be formed, the solventthereof is neutralized with an acid before the precipitate is separated.11. The process for producing the resin additive composition as setforth in claim 8, which comprises blending a solution or suspension ofsaid functional ingredient(s) in a solvent containing an alcohol and asolution of a calix(n+m+l)arene represented by the above general formula(2) in a solvent containing an alcohol, followed by neutralizing themixed solution with an acid, whereby a precipitate is caused to beformed, and separating and drying the resulting precipitate.
 12. Theprocess for producing the resin additive composition as set forth inclaim 8, which comprises blending a solution or suspension of saidfunctional ingredient(s) in a solvent containing an alcohol and asolution of a calix(n+m+l)arene represented by the above general formula(2) in a solvent containing an alcohol, followed by adding to theresulting mixture an organic poor solvent miscible with water and/or analcohol, or water, whereby a precipitate is caused to be formed, andseparating and drying the resulting precipitate.
 13. The process forproducing the resin additive composition as set forth in claim 8, whichcomprises blending a solution or suspension of said functionalingredient(s) in a solvent containing an alcohol and a solution of acalix(n+m+l)arene represented by the above general formula (2) in asolvent containing an alcohol, followed by evaporating the solvent fromthe mixture, whereby a precipitate is caused to be formed, andseparating and drying the resulting precipitate.
 14. The process forproducing the resin additive composition as set forth in claims 12 or13, wherein after a precipitate has been caused to be formed, thesolvent thereof is neutralized with an acid, and then the precipitate isseparated.
 15. The process for producing the resin additive compositionas set forth in claim 8, which comprises adding dropwise with stirring asolution of a calix(n+m+l)arene represented by the above general formula(2) in a solvent containing an alcohol to a solution or suspension ofsaid functional ingredient(s) in a solvent miscible with an alcohol,whereby a precipitate is caused to be formed, and filtering andseparating the resulting precipitate.
 16. A resin composition in whichthe resin additive composition as set forth in any one of claims 1-6 hasbeen incorporated.
 17. The resin composition as set forth in claim 16which has been subjected to thermal plasticizing treatment or thermalcuring treatment.